Anion Adsorption at the Inner‐Helmholtz Plane Directs Cathode Electrolyte Interphase Formation

Abstract Constructing a stable cathode‐electrolyte‐interphase (CEI) on cathode surface constitutes the foundation of realizing high‐voltage Li‐ion batteries, yet its formation, a highly heterogeneous process involving irreversible reactions between electrolyte components and cathode materials, remains poorly understood. Herein, combining multiple in situ / operando interfacial characterization techniques, we establish the correlation between interfacial structure and interphasial chemistry, and reveal the key role played by adsorptive behavior of various electrolyte components in the inner‐Helmholtz plane during CEI formation. Quartz crystal microbalance equipped with dissipation modification detects that difluorooxalatoborate (DFOB − ) anion preferentially adsorbed on LiCoO 2 tends to expel carbonate solvents from the adsorption layer, thus suppressing their electrochemical decomposition at high voltages and leading to a more compact CEI derived from anions with limited contribution from organic ingredients. Consequently, the CoO 2 lattice structure protected by the dense CEI remains intact despite near‐complete delithiation, thereby ensuring excellent cycling stability for 4.7 V operation of LiCoO 2 cathode. The atomistic‐level insight into the key factors that govern CEI formation provides directive knowledge that accelerates electrolyte design for high‐voltage batteries.

Authors

Institutions

Publication Details

Journal
Angewandte Chemie
Published
2025-02-26
DOI
https://doi.org/10.1002/ange.202425535
Citations
4
Primary Topic
Membrane-based Ion Separation Techniques
Type
article
Field-Weighted Citation Impact
2.70
Controls
|||
ALL TIME
JAN
FEB
MAR
APR
MAY
JUN
JUL
AUG
SEP
OCT
article

Anion Adsorption at the Inner‐Helmholtz Plane Directs Cathode Electrolyte Interphase Formation

Tao Shen, Zu‐Wei Yin, Shida Xue, Kunchen Xie et al.
4 citations
Angewandte Chemie
Membrane-based Ion Separation Techniques
2.70
article

Anion Adsorption at the Inner‐Helmholtz Plane Directs Cathode Electrolyte Interphase Formation

Tao Shen, Zu‐Wei Yin, Shida Xue, Kunchen Xie, Jimin Qiu, Feng Ming Pan, Zihang Dong, Xudong Zhao, Guorui Zheng, Yuxiang Huang, Jianjun Fang, Haoyu Xue, Luyi Yang, Kai Yang, Peng‐Hu Du, Peng Liu, Kang Xu, Shiqi Liu, Hai Lin, Shiming Chen, Yuchen Ji, Aimin Cao
article en
4 citations

Abstract

Abstract Constructing a stable cathode‐electrolyte‐interphase (CEI) on cathode surface constitutes the foundation of realizing high‐voltage Li‐ion batteries, yet its formation, a highly heterogeneous process involving irreversible reactions between electrolyte components and cathode materials, remains poorly understood. Herein, combining multiple in situ / operando interfacial characterization techniques, we establish the correlation between interfacial structure and interphasial chemistry, and reveal the key role played by adsorptive behavior of various electrolyte components in the inner‐Helmholtz plane during CEI formation. Quartz crystal microbalance equipped with dissipation modification detects that difluorooxalatoborate (DFOB − ) anion preferentially adsorbed on LiCoO 2 tends to expel carbonate solvents from the adsorption layer, thus suppressing their electrochemical decomposition at high voltages and leading to a more compact CEI derived from anions with limited contribution from organic ingredients. Consequently, the CoO 2 lattice structure protected by the dense CEI remains intact despite near‐complete delithiation, thereby ensuring excellent cycling stability for 4.7 V operation of LiCoO 2 cathode. The atomistic‐level insight into the key factors that govern CEI formation provides directive knowledge that accelerates electrolyte design for high‐voltage batteries.

Angewandte ChemieVol. 137(20)
King University (US), Xiamen University (CN), Peking University (CN), University of Surrey (GB), Beijing University of Technology (CN), Biolin Scientific (United Kingdom) (GB), Tsinghua–Berkeley Shenzhen Institute (CN), Ai Corporation (United Kingdom) (GB), Institute of Materials Research of the Slovak Academy of Sciences (SK), Peking University Shenzhen Hospital (CN), Division of Materials Science and Engineering (AU), Tsinghua University (CN)
Openalex Percentile: Top 11%
Membrane-based Ion Separation Techniques
2.70
DOIOpen Access PDFOpenAlex
AI Navigator

Ask Laika to Summarize, Analyze, and Connect papers live on the map.

Summarize Papers & Methodologies

Extract key findings, datasets, and comparative methods across publications.

Benchmark Rankings & Visual Analytics

Rank top research institutions, authors, funders, topics, and journals by Field-Weighted Citation Impact (FWCI) and paper volume with instant charts.

Connect Distant Disciplines

Bridge topological clusters on the map to find hidden collaborative intersections.